A chemical process of separating olefins from aluminum alkyls by forming complexes of the aluminum alkyls which are insoluble in the olefins

ABSTRACT

It is disclosed that olefins can be readily separated from aluminum alkyls and related compounds by forming complexes of the aluminum alkyls which are insoluble in the olefins. Two liquid phases that form on standing are readily separated by decantation. The insolubility condition is enhanced by the absence of light olefins hence the separation is particularly applicable to dodecene and higher olefins because lower olefins are readily separated from aluminum alkyls by distillation and because the higher olefins are less miscible with the complexes. An important aspect of the present disclosure is the avoidance of any need for pyrolysis cleavage of complexes.

United States Patent Kobetz Sept. 5, 1972 I A CHEMICAL PROCESS OF 2,787,626 4/] 1957 Redman ..260//448 J M 2,826,598 3 1958 Ziegler et al ..260 448 SEPARATING OI EFINS FRO 3,384,651 5/1968 Davis ..260/498 I0 I F,

ALUMINUM ALKYLS BY FORMING COMPLEXES OF THE ALUMINUM ALKYLS WHICH ARE INSOLUBLE IN THE OLEFINS Inventor; Paul Kobetz, Baton Rouge,

Corporation, New York,-

Assignee: Ethyl N.Y.

Filed: Aug. 24, 1970 Appl. No.: 66,437

References Cited UNITED STATES PATENTS 12/ 1 968 Ziegenhain ..260/448 Ziegler etal "zoo/553.1 5 r A k 7,

Primary Examiner-Delbert E. Gantz Assistant Examiner-J. M. Nelson Atmmey-Donald L. Johnson, John F. Sieberth, Shelton B. McAnelly and Arthur G. Connolly [57] ABSTRACT It is disclosed that olefins can be readily separated from aluminum alkyls and related compounds by forming complexes of the aluminum alkyls which are insoluble in the olefins. Two liquid phases that form on standing are readily separated by decantation. The insolubility condition is enhanced by the absence of light olefins hence the separation is particularly applicable to dodecene and higher olefins because lower olefins are readily separated from aluminum alkyls by distillation and because the higher olefins are less miscible with the complexes. An important aspect of the present disclosure is the avoidance of any need for pyrolysis cleavage of complexes.

20 Claims, 4 Drawing figures CHEMICAL PROCESS OF SEPARATING OLEFINS FROM ALUMINUM ALKYLS BY FORMING COMPLEXES OF THE ALUMINUM ALKYLS WHICH ARE INSOLUBLE IN THE OLEFINS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to complexes of organo aluminum compounds and in particular to the recovery of aluminum alkyls from olefins with the use of such complexes and to the separation of olefins from such complexes. In a further aspect the present invention relates to the preparation of higher alkyl aluminum trialkyls and olefins by polymerization, or chain growth or, generally, a synthesis operation with olefins on organo aluminum compounds or complexes of such compounds and wherein alkali metal halide and related complexes of aluminum alkyls are used to facilitate recovery of organo aluminum compounds from mixtures thereof with olefins.

2. Description of the Prior Art Higher alkyl trialkyl aluminums and olefins are readily produced from light olefins by synthesis reactions using various catalysts such as lower alkyl trialkyl aluminums, typically triethyl, tripropyl, tributyl and trioctyl aluminum and mixtures thereof. A typical catalytic olefin synthesis reaction process is disclosed in US. Pat. No. 2,781,410 wherein only catalytic quantities of alkyl aluminum compounds are required in which instance, the olefins may be recovered by hydrolyzing the aluminum alkyls. The loss of the aluminum alkyls in this manner is generally tolerated.

Another procedure for producing olefins is by a stoichiometric chain growth operation of lower olefins such as ethylene or propylene or mixtures thereof on aluminum alkyl compounds as typified in the foregoing followed by a second step operation of displacement with ethylene or propylene to liberate higher olefins and regenerate triethyl aluminum for recycle to the chain growth operation. In this operation the amount of aluminum alkyl involved is so great that the loss thereof in a hydrolysis operation is not economically feasible making it necessary to recover the aluminum alkyls or at least a major portion thereof for recycle. The prior art in this area has been characterized and limited by the knowledge that the separation of aluminum trialkyl from certain olefins is a difficult proposition by ordinary low-cost techniques such as distillation inasmuch as the boiling point of triethyl aluminum is close to the boiling points of the olefins, l-dodecene and ltetradecene. Thus, efficient separations are difficult requiring elaborate distillation facilities.

Various efforts have been made in the past to employ 5 2:1 and 1:1 complexes of aluminum alkyls with electron donor compounds such as NaF and KP and other complexing agents discussed herein to assist in the separations of aluminum alkyls and olefins; however, the recovery of aluminum alkyls by the usual pyrolysis cleavage of complexes having a higher amount of combined aluminum alkyl to produce free aluminum alkyls plus complexes having a lower amount of aluminum alkyl or no aluminum alkyl is not a simple operation and is frequently accompanied by degrading reactions due to the rather severe conditions required.

Several types of prior art processing involving complexing and cleavage for separations of aluminum alkyls and olefins are described in US. Pat. No. 3,415,862 and the references cited therein; however, the process discussed in the patent involves a fractionation of higher aluminum alkyls from complexes involving lower alkyls. Olefins present in such mixtures seemingly would be fractionated with the higher alkyls and would not be separated. The process of the patent is characterized by the difficulty that a pyrolysis or thermal cleavage is involved which must be performed under comparatively severe conditions conducive to side reactions which cause losses of desired materials.

OBJECTS AND DRAWING It is accordingly an object of the present invention to provide a procedure for recovering aluminum alkyls from admixture with olefins by forming complexes of the aluminum alkyls which are readily separable from the olefins on a solubility basis by simple decantation techniques.

Another object of the present invention is to provide a combined procedure for producing olefins by chain growth operations with lower olefins wherein the chain growth operation is conducted using a catalytic or a stoichiometric growth medium which is a complex of aluminum trialkyl and an alkali metal halide and wherein the olefins are recovered by processing involving the step of decantation separation of immiscible olefins from the aluminum alkyl complexes.

Other and further objects and features of the present v invention will become apparent upon a careful consideration of the following discussion and drawing wherein:

FIG. 1 shows a preferred embodiment of the present invention.

FIG. 2 shows a variation of the present invention wherein light olefins are distilled from complexes.

FIG. 3 shows a method of forming mixtures of olefins and triethyl aluminum to be separated in accordance with the present invention.

FIG. 4 shows an olefins process wherein complexes used in the separation of olefins are recovered and recycled to a synthesis type of operation to generate additional olefins.

SUMMARY OF THE INVENTION The present invention relates to a process for recovering olefins having from about 12 to about 30 carbon atoms per molecule from admixture with triethyl aluminum or tripropyl aluminum or mixtures thereof. In the process there is formed a mixture of l) the olefins and (2) a 2:1 molar complex of thetrialkyl aluminum and a complexing agent MX of the form: 2(R) AlzMX wherein M is alkali metal; X is halogen, cyanide, phenoxy, methoxy, cyanate or azide, iliiiisstl yi or, 992x 1. w

The mixture formed is subjected to a phase separation to produce two liquid phases, one phase enriched in olefins having from about 12 to about 30 carbon atoms per molecule, the other phase enriched in a 2:1 molar complex of trialkyl aluminum and MX.

Preferred M components of the complexes 2(R") AlzMX are sodium, potassium and mixtures containing various proportions of sodium and potassium such as 3/1, U1, 1/3 on a molar basis.

Preferred X components of the complexes 2(R") AlzMX are fluoride, cyanide, phenoxy, methoxy, cyanate and azide.

Preferred specific MX components of the complexes 2(R)3 AlzMX are sodium fluoride, sodium phenoxide, um methoxide. nd s iuinrqxan rqe-m.

Preferably, the recovery of the present process is from olefin-aluminum alkyl mixtures wherein the aluminum alkyl consists essentially of triethyl aluminum.

In another aspect the recovery of the present process is from olefin-aluminum alkyl mixtures wherein the aluminum alkyl consists essentially of tripropyl aluminum.

In a particularly preferred embodiment of the present process the complex formed is a 2:1 molar complex of triethyl aluminum and sodium fluoride.

Preferably, the phase separation is density-based using operations such as settling, decantation and centrifuging.

A preferred process in accordance with the present invention recovers olefins having from about four to about 30 carbon atoms per molecule from admixture with triethyl aluminum. In the process there is formed a mixture of l) the olefins and (2) a 2:1 molar complex oftriethyl aluminum and a complexing agent MX of the form: 2Et Al:MX wherein M is alkali metal; X is halogen, cyanide, phenoxy, methoxy, cyanate or azide.

The mixture formed is then distilled to remove light olefins up to about decene, inclusive, and the remaining mixture is subjected to a phase separation to produce two liquid phases, one phase enriched in olefins having from about 12 to about 30 carbon atoms per molecule, the other phaseenriched in a 2:1 molar complex of triethylaluminum and MX. The distillation is under conditions which avoid the conversion of the 2:1 molar complex into a 1:1 molar complex.

A particularly preferred process in accordance with the present invention is an aluminum chemistry process for producing olefins having from about four to about 30 carbon atoms per molecule from lower olefins having up to about sixcarbon atoms per molecule. This process involves chain growing with a lower olefin having from about two to about six carbon atoms per molecule and the complex 2Et Al:MX to produce a higher alkyl aluminum complex of the formula 2R Al:MX wherein R has from about two to about 30 carbon atoms per radical, M is alkali metal; X is halogen, cyanide, phenoxy, methoxy, cyanate or azide.

The chain growth product is subjected to displacement whereby is produced (1) olefins having a number of carbon atoms per molecule corresponding to the number of carbon atoms in the R radicals and (2) a 2:1 molar complex of triethyl aluminum and MX.

The mixture from the displacement is distilled to remove light olefins up to about decene, inclusive, the distillation is under conditions which avoid the conversion of the 2: 1 molar complex into a 1 :1 complex.

The mixture remaining after the distillation is subjected to a phase separation to produce two liquid phases, one phase enriched in olefins having from about 12 to about 30 carbon atoms per molecule, the other phase enriched in a 2:1 molar complex of triethylaluminum and MX.

The 2: 1 molar complex of triethyl aluminum and MX recovered from the phase separation is preferably recycled to the chain growing step.

The distillation of olefins is performed at a temperature from about C. to aboutl75 C. and at a pressure from about 1 to about 70 millimeters of mercury absolute pressure. Preferred distillation conditions are from about C. to about C. and from'2 to about 20 millimeters of mercury absolute pressure. Typical highly preferred conditions are a flash at about 1 10 C. and at a pressure of about 15 millimeters of mercury absolute.

In accordance with the teachings of the present invention, a lower olefin such as ethylene or propylene is reacted with an aluminum alkyl R" Al or an aluminum alkyl complex of the formula 2(R Al:MX at a temperature from about 90C. to about 160 C. and a pres! sure of 500 to about 3,000 pounds per square inch for a time from about 1 minute to about 20 hours whereby the alkyl groups of the starting complex are converted to higher alkyl groups R- or (C l-1 having up to about 30 carbon atoms per radical. The amount of thelower olefin reacted is from about 0.01 to about 100 mols per alkyl radical R" of the starting complexes. Further. information in the area of chain growth is contained in U.S. Pat. Nos. 2,826,598; 3,384,651 and 3,415,861. The production of alkyl aluminum com-- pounds such as triethyl aluminum and tripropyl aluminum is discussed in U.S. Pat. Nos. 2,787,626 and 2,885,314.

Following the foregoing chain growth operation, the product thereof is-reacted with a lower olefin such as ethylene orpropylene in a displacement type of reaction at a temperature from about 260 C. to about 325 C. and a pressure from about to about 250 psig to convert the grown radicals R- to olefins of the formula R(I-I)H or C H The result of the displacement operation is the production of a mixture containing olefins having from about four to about 30 carbon atoms per molecule plus a regenerated lower alkyl trialkyl aluminum or lower alkyl trialkyl aluminum complex suitable for recycle to the first step operation for repeated growth.

Suitable recycle together with effective recovery of the product olefins requires a separation step which has been a fundamental problem throughout the art of handling of mixtures of olefins and aluminum alkyl materials. In the present process utilization is made of the discovery that certain simple decantation separations of aluminum alkyls and olefins are readily performed without the need for the severe conditions which characterize pyrolysis of 2:1 complexes to produce 1:1 complexes. To this end present process involves a distillation removal of light olefins having up to about 10 carbon atoms per molecule from the mixture of olefins and complex or from the olefins and aluminum alkyls prior to the formation of the complex. The resultant mixture of heavy olefins having from about 12 to about 30 carbon atoms per molecule and complex forms two distinct liquid phases which are readily separated by a simple density based decantation or centrifuging operation. The result of the decantation separation therefore is the production of a stream of heavy olefins having from about 12 to about 30 carbon atoms per molecule and a stream of the separated complex suitable for return to the chain growth operation or other utilization. The olefins are useful in numerous ways such as the preparation of detergents; for example, by reaction with $0 to produce sulfonates.

Further purification of the olefins obtained from the decantation operation typically involve a hydrolysis operation in which residual quantities of the complex are removed from the olefins through the use of water or various chemical washing agents such as dilute aqueous' caustic (NaOH in about 5-30 wt. percent concentration).

Further treatment and purification operations of the olefins may; include distillation operations wherein the olefins are dehydrated to remove residual quantities of water from the purification operations and wherein the olefins are categorized into various fractions on a basis of molecular weight or number of carbon atoms per molecule.

It is significant to observe that in the foregoing described process there is no need to pyrolyze complexes of one structure such as 2:1 to form complexes having a different ratio of the constituents such as 1:1. The operations of displacement with lower olefins and of distillation of the displacement products to remove the lighter olefins ranging up to about decene are conveniently performed at low temperatures in low cost brief contact flash distillations wherein degradation of the materials present is held to a minimum.

With reference now to FIG. 1 of the drawing, the apparatus shown therein indicates a first step of forming which produces a mixture of trialkyl aluminum and olefins wherein the olefins typically range from about four to about 30 carbon atoms per molecule. The forming step 10 is of several different arrangements such as chain growth, polymerization, displacement of branched alkyl alkyl aluminum compounds such as TIBA, hydroalumination with and without olefins being present, etc.

Thus, the olefins from the forming step 10 typically contain olefins in one or more of several different molecular weight categories which are light olefins up to about decene, dodecene and tetradecene and some olefins that are higher than tetradecene. The present processing provides for components of all molecular weight. In specific instances some of such provision may not be needed. The mixture of aluminum alkyls and olefins from the forming step is preferably subjected to distillation at 11 at which point the lighter olefins having up to about 10 carbon atoms per molecule are removed leaving a mixture containing heavier olefins having from about 12 to 30 carbon atoms per molecule and also containing aluminum alkyl materials from the forming step. The mixture from distillation l l is then combined with a complexing agent MX in the combining step 12 in such proportions as to produce a 2:1 molar complex of the aluminum alkyls contained in the stream from distillation 11 with the complexing agent MX. In this complex, M is alkali metal, such as sodium, potassium or lithium; X is halogen, such as fluoride, cyanide, phenoxy, methoxy, cyanate or azide.

The complex formed is immiscible with the olefins so that on standing a system is produced containing two separate liquid phases of different density and consequently which readily separate. Separation of the phases is performed at 13 to yield an olefin stream containing olefins ranging from about dodecene to about eicosene plus a separate aluminum alkyl complex phase 2(R) Al:MX.

FIG. 2 shows an alternate to FIG. 1 wherein the sequence of the distillation 11 and the combining step 12 is reversed. In some instances this particular sequence is desirable because of the fact that in tying up the aluminum alkyls as complexes prior to the distillation, it is possible to distill olefins that would otherwise be impossible to remove from the aluminum alkyls by distillation. Thus, in the apparatus of FIG. 2, it is possible to remove olefins higher than decene such asdodecene and tetradecene by the distillation 11.

FIG. 3 indicates a typical method of forming the mix,-

I ture of olefins and aluminum alkyls in the step 10 of FIGS. 1 and 2. The particular type of forming step typified includes a chain growth operation 14 and an ethylene displacement operation 15. As is well known the chain growth operation includes a reaction of aluminum alkyls to produce higher alkyl groupsvattached to aluminum. It may also be aluminum alkyl complexes with MX as defined herein. The higher alkyl groups include individuals or mixtures of two or more ranging from about butyl through about eicosyl. The aluminum alkyl compounds from the chain growth are then subjected to a displacement operation 15 with ethylene or propylene whereby olefins corresponding to the alkyl groups of the growth product are liberated forming R" Al, typically triethyl aluminum or tripropyl aluminum or mixtures thereof suitable for recycle to the chain growth operation 14 for additional growth. The problem, of course, with such recycle is that olefins thus produced in the mixture from the ethylene displacement 1S usually include dodecene and tetradecene which boil close to the boiling point of triethyl aluminum making a simple distillation separation impossible. FIG. 4 shows a recycle arrangement by means of which the inherent difficulty of separation of certain olefins and certain trialkyl aluminum is avoided.

With reference now to FIG. 4 of the drawing, theapparatus shown therein includes a sequence of chain growth 14 and ethylene displacement 15 in forming step 10, combining 12, distilling 11 and separation 13, all of which correspond substantially to the steps of similar reference characters discussed in connection with FIGS. 1, 2 and 3. The significance of FIG. 4 is that it shows a recycle of the complex from the separation step 13 to the chain growth 14 to permit a chain growth operation upon the recycle 2(R) Al:MX complexes. In this instance, the combining step 12 is largely a mixer for the convenient insertion of make-up trialkyl aluminum and MX complex.

Lighter olefins having from about four to about 12 carbon atoms per molecule are removed in distillation 11 following which the phase separation discussed in the foregoing occurs at 13 to yield higher olefins having from about 14 through about 30 carbon atoms per molecule plus the complex 2(R") Al:MX which is recycled to chain growth.

It is, of course, evident that the particular method of supplying the make-up alkyl aluminum and complexing agent is subject to some variation in that it is suitably supplied either as separate components of trialkyl aluminum and complexing agent or as a preformed complex of two molecules of trialkyl aluminum and complexing agent and that the components or the preformed complex may be fed at any appropriate point in the recirculation loop shown.

Preferred complexes because of their solubility characteristics are: 2-triethylaluminumzsodium fluoride, 2-triethylaluminum:potassium fluoride, 2- triethylaluminumzpotassium phenoxide, 2-tripropylaluminumzsodium cyanide, 2-tripropylaluminumzsodium phenoxide, 2-tripropylaluminum:sodium fluoride, 2- triethylaluminum:potassium cyanide, Z-tripropylaluminumzpotassium cyanide.

Other preferred complexes are: 2-triethylaluminum, 1/2 sodium cyanide, l/2 potassium cyanide Z-tripropylaluminum, l/4' sodium cyanide, 3/4 potassium cyanide Z-triethylaluminum, 1/2 sodium fluoride, 1/ 2 potassium fluoride I 2-tripropylaluminum, l/4 sodium fluoride, 3/4 potassium fluoride I 2-triethylaluminum, sodium cyanate 2-tripropylaluminum, sodium cyanate Z-triethylaluminum, potassium cyanate 2-tripropylaluminum, potassium cyanate Z-triethylaluminum, sodium phenoxide 2-tripropylaluminum, potassium phenoxide 2-triethylaluminum, sodium methoxide 2-tripropylaluminum, sodium methoxide 2-triethylaluminum, potassium ethoxide 2-tripropylaluminum, potassium ethoxide Z-triethylaluminum, sodium methyl phenoxide Z-tripropylaluminum, potassium methyl phenoxide 2-triethylaluminum, sodium azide Z-triethylaluminum, potassium azide 2-tripropylaluminum, sodium azide 2-tripropylaluminum, potassium azide 2-tripropylaluminum, l/2 sodium azide, 1/2 potassium azide 2-triethylaluminum, l/2 sodium azide, l/2 potassium azide 2-triethylaluminum, l/2 sodium cyanate, l/2 potassium cyanate 2-tripropylaluminum, l/2 sodium cyanate, l/2 potassium cyanate 2-triethylaluminum, 1/2 sodium phenoxide, 1/2 potassium phenoxide 2-tripropylaluminum, l/2 sodium phenoxide, l/2 potassium phenoxide Z-triethylaluminum, potassium methoxide 2-tripropylaluminum, potassium methoxide The following examples indicate preferred embodiments and aspects of the present invention and are presented in an exemplary, but not limiting, sense.

EXAMPLE I 37.0 Grams (g) of the complex 2Et Al-NaF was added to 31 g of dodecene (40 cc) at 30 C. and stirred about minutes. The mixture was allowed to settle into two layers. A sample of the upper, olefin, layer was taken, analyzed and found to contain 4.5 wt. percent 2(Et) Al:NaF.

EXAMPLE ll Example I was repeated in a duplicate run. The olefin layer contained 5.1 wt. percent 2(Et) Al:NaF.

EXAMPLE III Example 1 was repeated using a complex of the type 1.8 (Et) Al:NaF. The olefinlayer contained 11.0 wt. percent 1.8 (Et) Al:NaF.

EXAMPLE IV Example 111 was repeated using octene-l at 0 C. The olefin layer contained 1 1.0 wt. percent of the complex, 1.8 (Et) Al:NaF. Examples 111 and IV show the undesirably higher solubility of complexes containing less than. 2 mols of R" AI'per mol of complexing agent in comparison to the 2:1 molar complexes of Examples 1 and I1.

EXAMPLE V Example I was repeated in several runs using a complex of 2 Et AlzNacN. The solubility of the complex was 1.5-2.0 wt. percent in the olefins.

EXAMPLE VI Example I is repeated in several runs using a complex of 2(propy1) Al:NaF. Similar results are obtained.

EXAMPLE VII Example I was repeated using 0.2 mols of triethyl aluminum, 0.1 mol of potassium fluoride, and 40 cc of dodecene-l at 25 C. The olefin layer contained approximately 3.0 wt. percent of the complex.

EXAMPLE vm Example I was repeated using 16.8 grams of triethylaluminum and 3.7 grams of NaCN (2:1 mol ratio), using 40 cc of dodecene-l. It was stirred 20 minutes at C. A 5 cc sample of the top layer was withdrawn and analyzed. It contained 2.5 wt. percent of the complex.

EXAMPLE IX Example I was repeated using 19.4 grams of triethylaluminum and 10 grams of sodium phenoxide (2:1 mol ratio). These were heated to 100 C. for about 10 minutes and mixed to form a complex having a melting point of about 45 C.

Fifty grams of hexadecene-l was added to the preformed complex at 60 C. and stirred for 10 minutes. The mixture was allowed to settle and a 10 cc sample taken of the supernatant liquid and analyzed. It contained 1.4 wt. percent of the complex.

The mixture was heated to 100 C. and again mixed and then allowed to settle while maintaining a temperature of 100 C. Another 10 cc sample of the supernatant liquid was taken and analyzed. It contained 5.5 wt. percent of the complex.

EXAMPLE X Example IX is repeated using sodium methoxide. Similar results are obtained.

EXAMPLE XI Example IX is repeated using 2Et A1:NaN(Cl-I Similar results are obtained.

9 EXAMPLE x11 EXAMPLE XIII 1/2 M01 (57 grams) of triethyl aluminum is added to a mixture of olefins ranging from butene to about eicosene to form a clear solution. The solution is flash distilled at 170 at atmospheric pressure removing decene.

To the residue of dodecene and higher molecular weight oleflns and triethyl aluminum is added 1/4 mol (12.75 grams) of sodium cyanide. The mixture is heated at 70 C. for 1 hour to form the substantially insoluble complex 2(Et) Al:NaCN.

The mixture is cooled to 30 C. and allowed to settle into two liquid phases. The upper phase is sampled and analyzed. It contains the C and higher m-w oleflns plus 1 to 2 wt. percent of the complex.

The phases are separated by decantation to provide one phase enriched in oleflns having from about 12 to about 30 carbon atoms per molecule and another phase enriched in 2(Et) Al:NaCN. The latter contains a small amount of olefins, less than about 10 percent by weight.

EXAMPLE XIV Example XIII is repeated using 2(Et) Al:NaF. Similar results are obtained; however, the solubility of the 2(Et) Al:NaF complex in the oleflns is higher than the solubility of the complex of Example XIII.

EXAMPLE XV 40 cc of tetradecene-1 was added to 10.3 grams of the complex 2(Et) Al:NaCN at a pot temperature of 135 C. and a vapor temperature of 110 C. at a pressure of approximately 5 millimeters of mercury.

A part of the mixture was vaporized from the pot without using a rectification column in a simple flash distillation to yield an overhead of 30 cc containing a negligible 0.45 wt. Percent of the complex.

This shows that tetradecene can be flash distilled from the typical complex of the example.

The remaining mixture still containing some olefins was cooled to room temperature and allowed to settle forming two liquid phases.

EXAMPLE XVI Example XV was repeated with hexadecene. The distillate under the same conditions contained approximately 5 wt. percent 2(Et) Al:NaCN. Examples XV and XVI together show that a distillation of the complex is practical to remove light olefins up to about tetradecene.

EXAMPLE XVII 24.6 Grams of 2(Et) Al:NaF was added to 129 grams of toluene in a l-liter stirred Parr reactor and heated at l46-1 5 C. at an ethylene pressure of 1,000 psig. After 12 hours the reactor was opened and analyzed for olefins. Approximately 230 grams of oleflns containing higher than 90 percent vinyl oleflns was obtained. The oleflns were analyzed by Vapor Phase Chromatography up through the dodecene content showing the following distribution normalized percent. In a more complete analysis, the higher olefins above dodecene would show up in progressively smaller amounts.

The free oleflns up through decene-l, inclusive, are flashed as in foregoing examples. The residue of complex and oleflns higher than decene-l is allowed to settle forming two phases, an upper phase essentially of oleflns and a lower phase essentially of complex. The separation is improved where the R- groups of the complex are higher then ethyl or propyl by displacing the longer groups with ethylene or propylene prior to the distillation.

Iclaim:

1. A process for recovering oleflns having from about 12 to about 30 carbon atoms per molecule from admixture with triethyl aluminum or tripropyl aluminum or mixtures thereof which comprises:

a. forming a mixture of (1) said oleflns and (2) a 2:1

molar complex of said trialkyl aluminum and a complexing agent MX of the form:

wherein M is alkali metal; X is halogen, cyanide, phenoxy, methoxy, cyanate or azide, said forming step including a distillation wherein oleflns having up to about 10 carbon atoms per molecule are removed from the mixture of oleflns and complex or from the oleflns and aluminum alkyls prior to the formation of the complex; and

b. subjecting the mixture to a phase separation to produce two liquid phases, one phase enriched in oleflns having from about 12 to about 30 carbon atoms per molecule, the other phase enriched in a 2:1 molar complex of trialkyl aluminum and MX. 2. The process of claim 1 wherein M sodium or potassium or a mixture thereof.

3. The process of claim 1 wherein M is sodium. 4. The process of claim 1 wherein X is fluoride, cyanide, phenoxy, methoxy, cyanate or azide.

5. The process of claim 1 wherein X is fluoride. 6. The process of claim 1 wherein X is phe'noxy. 7. The process of claim 1 wherein X is methoxy. 8. The process of claim 1 wherein MX is sodium fluoride.

9. The process of claim 1 wherein MX is sodium phenoxide.

10. The process of claim 1 wherein MX is sodium methoxide.

11. The process of claim 1 wherein MX is sodium cyanide.

12. The process of claim 1 wherein the phase separation is density based.

13. The process of claim 1 wherein the olefins are removed from admixture with triethyl aluminum.

14. The process of claim 1 wherein the oleflns are removed from admixture with tripropyl aluminum.

15. The process of claim 1 wherein the alkyl groups of the trialkyl aluminum are predominantly ethyl and MX is sodium fluoride.

16. A process for recovering olefins having from about four to about 30 carbon atoms per molecule from admixture with triethyl aluminum which comprises:

a. forming a mixture of 1) said olefins and (2) a 2:1

molar complex of said triethyl aluminum and a complexing agent MX of the form:

whereinM is alkali metal; X is halogen, cyanide,

phenoxy, methoxy, cyanate or azide, and distilling the mixture to remove light olefins up to about decene, then c. subjecting the remaining mixture to a phase separation to produce two liquid phases, one phase enriched in olefins having from about 12 to about 30 carbon atoms per molecule, the other phase enriched in a 2:1 molar complex of triethyl aluminum and MX, said distilling being under conditions which avoid the conversion of the 2:1 molar complex into a 1:1 molar complex.

17. An aluminum chemistry process for producing olefins having from about four to about 30 carbon atoms per molecule from lower olefins having up to about six carbon atoms per molecule, which comprises:

a-l. chain growing with a lower olefin having from about two to about six carbon atoms per molecule and the complex 2Et Al:MX to produce higher alkyl aluminum complex of the formula 2R Al:MX wherein R has from about two to about 30 carbon atoms per radical, M is alkali metal; X is halogen,

cyanide, phenoxy, methoxy, cyanate or azide; and

higher alkyl aluminum complexes of the foregoing step whereby is producedtl) olefins having a.

number of carbon atoms per molecule corresponding to the number of carbon atoms in the R radicals of the higher alkyl aluminum complexes, and (2) a 2:1 molar complex of triethyl aluminum and MX,

. distilling the mixture to remove light olefins up to about decene, then 0. subjecting the remaining mixture to a phase separation to produce two liquid phases, one phase enriched in olefins having from about 12 to about 30 carbon atoms per molecule, the other phase enriched in a 2:1 molar complex of triethylaluminum and MX, said distilling being under conditions which avoid the conversion of the 2:1 molar complex into a 1:1 complex, and

(1. recycling the 2:1 molar complex of triethylaluminum and MX from (21-2) to the chain growing step (a-l 18. The process of claim 16 wherein the distillation is at a temperature from about C. to about 175 C. and at a pressure from about 1 to about 70 mm of mercury absolute.

19. The process of claim 16 wherein the distillation is at a temperature from about C. to about 125 C, and at a pressure from about 2 to about 20 mm of mercu absolute.

ii). The process of claim 16 wherein the distillation is at a temperature of about C. and at a pressure of about 15 mm of mercury absolute. 

2. The process of claim 1 wherein M sodium or potassium or a mixture thereof.
 3. The process of claim 1 wherein M is sodium.
 4. The process of claim 1 wherein X is fluoride, cyanide, phenoxy, methoxy, cyanate or azide.
 5. The process of claim 1 wherein X is fluoride.
 6. The process of claim 1 wherein X is phenoxy.
 7. The process of claim 1 wherein X is methoxy.
 8. The process of claim 1 wherein MX is sodium fluoride.
 9. The process of claim 1 wherein MX is sodium phenoxide.
 10. The process of claim 1 wherein MX is sodium methoxide.
 11. The process of claim 1 wherein MX is sodium cyanide.
 12. The process of claim 1 wherein the phase separation is density based.
 13. The process of claim 1 wherein the olefins are removed from admixture with triethyl aluminum.
 14. The process of claim 1 wherein the olefins are removed from admixture with tripropyl aluminum.
 15. The process of claim 1 wherein the alkyl groups of the trialkyl aluminum are predominantly ethyl and MX is sodium fluoride.
 16. A process for recovering olefins having from about four to about 30 carbon atoms per molecule from admixture with triethyl aluminum which comprises: a. forming a mixture of (1) said olefins and (2) a 2:1 molar complex of said triethyl aluminum and a complexing agent MX of the form: (R'''')3Al:MX wherein M is alkali metal; X is halogen, cyanide, phenoxy, methoxy, cyanate or azide, and b. distilling the mixture to remove light olefins up to about decene, then c. subjecting the remaining mixture to a phase separation to produce two liquid phases, one phase enriched in olefins having from about 12 to about 30 carbon atoms per molecule, the other phase enriched in a 2:1 molar complex of triethyl aluminum and MX, said distilling being under conditions which avoid the conversion of the 2:1 molar complex into a 1:1 molar complex.
 17. An aluminum chemistry process for producing olefins having from about four to about 30 carbon atoms per molecule from lower olefins having up to about six carbon atoms per molecule, which comprises: a-1. chain growing with a lower olefin having from about two to about six carbon atoms per molecule and the complex 2Et3Al:MX to produce higher alkyl aluminum complex of the formula 2R3Al: MX wherein R has from about two to about 30 carbon atoms per radical, M is alkali metal; X is halogen, cyanide, phenoxy, methoxy, cyanate or azide; and a-2. subjecting to ethylene displacement at a temperature from about 260* C. to about 325* C. and a pressure from about 150 to about 250 psig, the higher alkyl aluminum complexes of the foregoing step whereby is produced (1) olefins having a number of carbon atoms per molecule corresponding to the number of carbon atoms in the R radicals of the higher alkyl aluminum complexes, and (2) a 2:1 molar complex of triethyl aluminum and MX, b. distilling the mixture to remove light olefins up to about decene, then c. subjecting the remaining mixture to a phase separation to produce two liquid phases, one phase enriched in olefins having from about 12 to about 30 carbon atoms per molecule, the other phase enriched in a 2:1 molar complex of triethylaluminum and MX, said distilling being under conditions which avoid the conversion of the 2:1 molar complex into a 1:1 complex, and d. recycling the 2:1 molar complex of triethylaluminum and MX from (a-2) to the chain growing step (a-1).
 18. The process of claim 16 wherein the distillation is at a temperature from about 80* C. to about 175* C. and at a pressure from about 1 to about 70 mm of mercury absolute.
 19. The process of claim 16 wherein the distillation is at a temperature from about 90* C. to about 125* C, and at a pressure from about 2 to about 20 mm of mercury absolute.
 20. The process of claim 16 wherein the distillation is at a temperature of about 110* C. and at a pressure of about 15 mm of mercury absolute. 